Gas phase ion chemistry and <i>ab initio</i> theoretical study of phosphine. III. Reactions of PH2+ and PH3+ with PH3

Antoniotti, Paola; Operti, Lorenza; Ragazzoni, Roberto; Tonachini, Glauco; Vaglio, Gian Angelo

doi:10.1063/1.480745

Cited by 5 publications

(3 citation statements)

References 38 publications

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“…All experiments were performed on a Finnigan ITMS mass spectrometer maintained at 333 K to obtain results comparable with studies of other systems . Ion trap mass spectrometry theory and methods are discussed in previous works. ,, Samples were admitted to the trap via an inlet system modified to permit the simultaneous introduction of three gases through different lines. Pressures measured with a Bayard Alpert ionization gauge were typically 2.0−10.0 × 10 -7 Torr for germane and ethene and about 5.0 × 10 -4 Torr for helium.…”

Section: Methodsmentioning

confidence: 99%

“…These studies also provide fundamental information on the behavior of selected ion species in the absence of perturbing effects, such as the presence of a solvent or counterions. , Combined experimental and theoretical investigation in the elucidation of gas-phase ion reaction mechanisms has the advantage of providing complementary information. − Mass spectrometry is used to describe the overall reactivity of gaseous systems and determine reaction mechanisms and kinetics of isolated ions, while ab initio calculations explore mechanistic details related to the experimental findings, such as the energetics and the structures of the ion intermediates, transition structures, and products.…”

Section: Introductionmentioning

confidence: 99%

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Experimental and Theoretical Study of the Formation of Germanium−Carbon Ion Species in Gaseous Germane/Ethene Mixtures

et al. 2001

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The gas-phase chemistry of gaseous germane/ethene mixtures has been investigated by ab initio theoretical calculations and by experiments to examine the formation and growth of germanium-/carbon-containing species. Ion/molecule reactions in GeH 4 /C 2 H 4 mixtures have been studied with an ion trap mass spectrometer. Ion abundance variations as a function of reaction time, reaction paths originating from primary ions of both reagents, and reaction rate constants of the main processes have been determined. The highest yield of new Ge-C bonds formed via reactions of Ge-containing ions with ethene molecules was obtained in mixtures carrying similar amounts of germane and ethene. Reactions of GeH 2 •+ with ethene play a prominent role in this system. High-level theoretical methods were therefore used to determine the geometrical structures and energies of transition structures, reaction intermediates, and final products for several reaction pathways. Formation of the adduct between GeH 2 •+ and H 2 CdCH 2 is the initial step. This process is fairly exothermic, and the free energy of the system allows several transformations. Isomerization pathways and H, H 2 , or CH 3 • loss pathways starting from this adduct have been explored. The free energy threshold defined by the first step shows that some transformations are likely to occur, whereas others can be regarded as inaccessible. Last, two theoretical methods have been used to compute the heats of formation of the attainable GeC 2 H n + species.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Study of the Formation of Germanium−Carbon Ion Species in Gaseous Germane/Ethene Mixtures

et al. 2001

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“…However, synthesis of compounds containing P−P bonds has proven to be much more challenging than synthesis of their carbon cousins . Thus, formation of P−P bonds by means of conventional chemical syntheses using organic phosphine monomers − requires carefully tuning the reaction conditions to harness formation of P−P compounds. Otherwise, undesired products, such as oxyacids and phosphorus oxides, will be obtained. ,, …”

Section: Introductionmentioning

confidence: 99%

Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism

et al. 2008

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A yellow solid material [P(x)H(y)] has been obtained in the reaction of phosphine (PH(3)) and nitric oxide (NO) at room temperature and characterized by thermogravimetric analysis mass spectrometry (TGA-MS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In this work using complete basis set (CBS-QB3) methods a plausible mechanism has been investigated for phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab initio method suggest (a) instead of the monomer the nitric oxide dimer acts as an initial oxidant, (b) the resulting phosphine oxides (H(3)P=O <--> H(3)P(+)O(-)) in the gas phase draw each other via strong dipolar interactions between the P-O groups, and (c) consequently an autocatalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations a series of cluster models was computed to simulate polymerization.

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Gas‐phase ion chemistry in germane–propane and germane–propene mixtures

et al. 2002

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Germane-propane and germane-propene gaseous mixtures were studied by ion trap mass spectrometry. Variations of ion abundances observed under different partial pressure ratios and mechanisms of ion-molecule reactions elucidated by multiple isolation steps are reported. In addition, the rate constants for the main reactions were experimentally determined and compared with the collisional rate constants to obtain the reaction efficiencies. The yield of ions containing both Ge and C atoms is higher in the germane-propene than in the germane-propane system. In the former mixture, chain propagation takes place starting from germane ions reacting with propene and proceeds with the formation of clusters such as Ge(2)C(4)H(n) (+) and Ge(3)CH(n) (+).

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Gas phase ion chemistry and ab initio theoretical study of phosphine. III. Reactions of PH2+ and PH3+ with PH3

Abstract: Gas phase ion chemistry and ab initio theoretical study of phosphine. I

Cited by 5 publications

References 38 publications

Experimental and Theoretical Study of the Formation of Germanium−Carbon Ion Species in Gaseous Germane/Ethene Mixtures

Experimental and Theoretical Study of the Formation of Germanium−Carbon Ion Species in Gaseous Germane/Ethene Mixtures

Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism

Gas‐phase ion chemistry in germane–propane and germane–propene mixtures

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